Procatalyst Composition with Substituted 1,2-Phenylene Aromatic Diester Internal Donor and Method

ABSTRACT

Disclosed are procatalyst compositions having an internal electron donor which include a substituted phenylene aromatic diester and optionally an electron donor component. Ziegler-Natta catalyst compositions containing the present procatalyst compositions exhibit high activity and produce propylene-based olefins with broad molecular weight distribution.

PRIORITY CLAIM

This application is a continuation of U.S. patent application Ser. No.12/650,834, filed on Dec. 31, 2009 which claims priority to U.S.provisional patent application Ser. No. 61/141,902, filed on Dec. 31,2008, the entire content of each is incorporated by reference herein.

BACKGROUND

The present disclosure relates to procatalyst compositions containing asubstituted phenylene aromatic diester internal electron donor and theincorporation of the same in catalyst compositions and the process ofmaking olefin-based polymers using said catalyst compositions.

Worldwide demand for olefin-based polymers continues to grow asapplications for these polymers become more diverse and moresophisticated. Known are Ziegler-Natta catalyst compositions for theproduction of olefin-based polymers. Ziegler-Natta catalyst compositionstypically include a procatalyst containing a transition metal halide(i.e., titanium, chromium, vanadium), a cocatalyst such as anorganoaluminum compound, and optionally an external electron donor.Ziegler-Natta catalyzed olefin-based polymers typically exhibit a narrowrange of molecular weight distribution. Given the perennial emergence ofnew applications for olefin-based polymers, the art recognizes the needfor olefin-based polymers with improved and varied properties. Desirablewould be Ziegler-Natta catalyst compositions for the productionolefin-based polymers that exhibit high catalyst activity duringpolymerization and produce propylene-based polymers with highisotacticity and broad molecular weight distribution.

SUMMARY

The present disclosure is directed to procatalyst compositionscontaining a substituted phenylene aromatic diester as an internalelectron donor and the application of the same in catalyst compositionsand polymerization processes. The substituted phenylene aromaticdiester-containing catalyst compositions of the present disclosuredemonstrate high activity during polymerization. In addition, thepresent substituted phenylene aromatic diester-containing catalystcompositions produce propylene-based olefins with high isotacticity andbroad molecular weight distribution.

In an embodiment, a process for producing a procatalyst composition isprovided. The process includes reacting a substituted phenylene aromaticdiester, a procatalyst precursor, and a halogenating agent. The reactionoccurs in a reaction mixture. The process includes forming a procatalystcomposition by way of halogenation. The procatalyst composition includesan internal electron donor composed of the substituted phenylenearomatic diester.

In an embodiment, a procatalyst composition is provided. The procatalystcomposition includes a combination of a magnesium moiety, a titaniummoiety and an internal electron donor. The internal electron donorincludes a substituted phenylene aromatic diester. The magnesium moietyand/or the titanium moiety may be a respective halide.

In an embodiment, the substituted phenylene aromatic diester has thestructure (I):

wherein R₁-R₁₄ are the same or different. Each of R₁-R₁₄ is selectedfrom hydrogen, a substituted hydrocarbyl group having 1 to 20 carbonatoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms,an alkoxy group having 1 to 20 carbon atoms, a heteroatom, andcombinations thereof. At least one of R₁-R₁₄ is not hydrogen.

In an embodiment, the structure (I) includes at least one of R₁-R₄selected from a substituted hydrocarbyl group having 1 to 20 carbonatoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms,and combinations thereof.

In an embodiment, the structure (I) includes at least one of R₅-R₁₄selected from a substituted hydrocarbyl group having 1 to 20 carbonatoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms,an alkoxy group having 1 to 20 carbon atoms, a heteroatom, andcombinations thereof.

The present disclosure provides another procatalyst composition. In anembodiment, a procatalyst composition is provided that includes acombination of a magnesium moiety, a titanium moiety and a mixedinternal electron donor. The mixed internal electron donor includes asubstituted phenylene aromatic diester and an electron donor component.

In an embodiment, the electron donor component is selected from aphthalate, an ethyl benzoate, a diether, and combinations thereof.

The present disclosure provides a catalyst composition. The catalystcomposition includes a procatalyst composition and a cocatalyst. Theprocatalyst composition includes a substituted phenylene aromaticdiester. In another embodiment, the catalyst composition can include amixed internal electron donor. The mixed internal electron donorincludes a substituted phenylene aromatic diester and an electron donorcomponent as disclosed above.

In an embodiment, the catalyst composition includes an external electrondonor, and/or an activity limiting agent.

The present disclosure provides a polymerization process. In anembodiment, a polymerization process is provided that includescontacting, under polymerization conditions, an olefin with a catalystcomposition. The catalyst composition includes a substituted phenylenearomatic diester. The process further includes forming an olefin-basedpolymer.

In an embodiment, the olefin is propylene. The process includes forminga propylene-based polymer having a polydispersity index from about 4.0to about 15.0.

In an embodiment, the olefin is propylene. The process includes forminga propylene-based polymer having a melt flow rate from about 0.01 g/10min to about 800 g/10 min.

An advantage of the present disclosure is the provision of an improvedprocatalyst composition.

An advantage of the present disclosure is the provision of an improvedcatalyst composition for the polymerization of olefin-based polymers.

An advantage of the present disclosure is a catalyst composition thatcontains a substituted phenylene aromatic diester, the catalystcomposition exhibiting improved activity during polymerization.

An advantage of the present disclosure is a catalyst composition with asubstituted phenylene aromatic diester that produces a propylene-basedpolymer with broad molecular weight distribution.

An advantage of the present disclosure is a catalyst composition thatcontains a substituted phenylene aromatic diester and has high catalystactivity and produces a propylene-based olefin with high isotacticity,and a broad molecular weight distribution.

DETAILED DESCRIPTION

In an embodiment, a process for producing a procatalyst composition isprovided. The process includes reacting a substituted phenylene aromaticdiester, a procatalyst precursor and a halogenating agent. The reactionoccurs in a reaction mixture. The reaction results in the formation of aprocatalyst composition. The procatalyst composition includes amagnesium moiety, a titanium moiety, and an internal electron donor. Theinternal electron donor includes the substituted phenylene aromaticdiester.

The substituted phenylene aromatic diester may be a substituted1,2-phenylene aromatic diester, a substituted 1,3-phenylene aromaticdiester, or a substituted 1,4-phenylene aromatic diester. In anembodiment, a 1,2-phenylene aromatic diester is provided. Thesubstituted 1,2-phenylene aromatic diester has the structure (I) below:

wherein R₁-R₁₄ are the same or different. Each of R₁-R₁₄ is selectedfrom a hydrogen, substituted hydrocarbyl group having 1 to 20 carbonatoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms,an alkoxy group having 1 to 20 carbon atoms, a heteroatom, andcombinations thereof. At least one of R₁-R₁₄ is not hydrogen.

As used herein, the term “hydrocarbyl” and “hydrocarbon” refer tosubstituents containing only hydrogen and carbon atoms, includingbranched or unbranched, saturated or unsaturated, cyclic, polycyclic,fused, or acyclic species, and combinations thereof. Nonlimitingexamples of hydrocarbyl groups include alkyl-, cycloalkyl-, alkenyl-,alkadienyl-, cycloalkenyl-, cycloalkadienyl-, aryl-, aralkyl, alkylaryl,and alkynyl- groups.

As used herein, the terms “substituted hydrocarbyl” and “substitutedhydrocarbon” refer to a hydrocarbyl group that is substituted with oneor more nonhydrocarbyl substituent groups. A nonlimiting example of anonhydrocarbyl substituent group is a heteroatom. As used herein, a“heteroatom” refers to an atom other than carbon or hydrogen. Theheteroatom can be a non-carbon atom from Groups IV, V, VI, and VII ofthe Periodic Table. Nonlimiting examples of heteroatoms include:halogens (F Cl, Br, I), N, O, P, B, S, and Si. A substituted hydrocarbylgroup also includes a halohydrocarbyl group and a silicon-containinghydrocarbyl group. As used herein, the term “halohydrocarbyl” grouprefers to a hydrocarbyl group that is substituted with one or morehalogen atoms. As used herein, the term “silicon-containing hydrocarbylgroup” is a hydrocarbyl group that is substituted with one or moresilicon atoms. The silicon atom(s) may or may not be in the carbonchain.

The procatalyst precursor can include (i) magnesium, (ii) a transitionmetal compound of an element from Periodic Table groups IV to VIII,(iii) a halide, an oxyhalide, and/or an alkoxide of (i) and/or (ii), and(iv) combinations of (i), (ii), and (iii). Nonlimiting examples ofsuitable procatalyst precursors include halides, oxyhalides, andalkoxides of magnesium, manganese, titanium, vanadium, chromium,molybdenum, zirconium, hafnium, and combinations thereof.

Various methods of making procatalyst precursors are known in the art.These methods are described, inter alia, in U.S. Pat. Nos. 6,825,146,5,034,361; 5,082,907; 5,151,399; 5,229,342; 5,106,806; 5,146,028;5,066,737; 5,077,357; 4,442,276; 4,540,679; 4,547,476; 4,460,701;4816,433; 4,829,037; 4,927,797; 4,990,479; 5,066,738; 5,028,671;5,153,158; 5,247,031; 5,247,032, and elsewhere. In an embodiment, thepreparation of the procatalyst precursor involves halogenation of mixedmagnesium and titanium alkoxides, and may involve the use of one or morecompounds, referred to as “clipping agents”, that aid in formingspecific, low molecular weight, compositions of the desired morphology.Nonlimiting examples of suitable clipping agents includetrialkylborates, especially triethylborate, phenolic compounds,especially cresol, and silanes.

In an embodiment, the procatalyst precursor is a magnesium moietycompound (MagMo), a mixed magnesium titanium compound (MagTi), or abenzoate-containing magnesium chloride compound (BenMag). In anembodiment, the procatalyst precursor is a magnesium moiety (“MagMo”)precursor. The “MagMo precursor” contains magnesium as the sole metalcomponent. The MagMo precursor includes a magnesium moiety. Nonlimitingexamples of suitable magnesium moieties include anhydrous magnesiumchloride and/or its alcohol adduct, magnesium alkoxide or aryloxide,mixed magnesium alkoxy halide, and/or carboxylated magnesium dialkoxideor aryloxide. In one embodiment, the MagMo precursor is a magnesiumdi(C₁₋₄)alkoxide. In a further embodiment, the MagMo precursor isdiethoxymagnesium.

In an embodiment, the procatalyst precursor is a mixedmagnesium/titanium compound (“MagTi”). The “MagTi precursor” has theformula Mg_(d)Ti(OR^(e))_(f)X_(g) wherein R^(e) is an aliphatic oraromatic hydrocarbon radical having 1 to 14 carbon atoms or COR′ whereinR′ is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbonatoms; each OR^(e) group is the same or different; X is independentlychlorine, bromine or iodine, preferably chlorine; d is 0.5 to 56, or 2to 4; f is 2 to 116 or 5 to 15; and g is 0.5 to 116, or 1 to 3. Theprecursors are prepared by controlled precipitation through removal ofan alcohol from the reaction mixture used in their preparation. In anembodiment, a reaction medium comprises a mixture of an aromatic liquid,especially a chlorinated aromatic compound, most especiallychlorobenzene, with an alkanol, especially ethanol. Suitablehalogenating agents include titanium tetrabromide, titaniumtetrachloride or titanium trichloride, especially titaniumtetrachloride. Removal of the alkanol from the solution used in thehalogenation, results in precipitation of the solid precursor, havingespecially desirable morphology and surface area. Moreover, theresulting precursors are particularly uniform in particle size.

In an embodiment, the procatalyst precursor is a benzoate-containingmagnesium chloride material (“BenMag”). As used herein, a“benzoate-containing magnesium chloride” (“BenMag”) can be a procatalyst(i.e., a halogenated procatalyst precursor) containing a benzoateinternal electron donor. The BenMag material may also include a titaniummoiety, such as a titanium halide. The benzoate internal donor is labileand can be replaced by other electron donors during procatalyst and/orcatalyst synthesis. Nonlimiting examples of suitable benzoate groupsinclude ethyl benzoate, methyl benzoate, ethyl p-methoxybenzoate, methylp-ethoxybenzoate, ethyl p-ethoxybenzoate, ethyl p-chlorobenzoate. In oneembodiment, the benzoate group is ethyl benzoate. Nonlimiting examplesof suitable BenMag procatalyst precursors include catalysts of the tradenames SHAC™ 103 and SHAC™ 310 available from The Dow Chemical Company,Midland, Mich. In an embodiment, the BenMag procatalyst precursor may bea product of halogenation of any procatalyst precursor (i.e., a MagMoprecursor or a MagTi precursor) in the presence of a benzoate compound.

The present procatalyst composition also includes an internal electrondonor. As used herein, an “internal electron donor” is a compound addedduring formation of the procatalyst composition that donates a pair ofelectrons to one or more metals present in the resultant procatalystcomposition. Not bounded by any particular theory, it is believed thatthe internal electron donor assists in regulating the formation ofactive sites and thus enhances catalyst stereoselectivity. In anembodiment, the internal electron donor includes a substituted phenylenearomatic diester of structure (I).

In an embodiment, the procatalyst precursor is converted to a solidprocatalyst by way of halogenation. Halogenation includes contacting theprocatalyst precursor with a halogenating agent in the presence of theinternal electron donor. Halogenation converts the magnesium moietypresent in the procatalyst precursor into a magnesium halide supportupon which the titanium moiety (such as a titanium halide) is deposited.Not wishing to be bound by any particular theory, it is believed thatduring halogenation the internal electron donor (1) regulates theposition of titanium on the magnesium-based support, (2) facilitatesconversion of the magnesium and titanium moieties into respectivehalides and (3) regulates the crystallite size of the magnesium halidesupport during conversion. Thus, provision of the internal electrondonor yields a procatalyst composition with enhanced stereoselectivity.

In an embodiment, the halogenating agent is a titanium halide having theformula Ti(OR^(e))_(f)X_(h) wherein R^(e) and X are defined as above, fis an integer from 0 to 3; h is an integer from 1 to 4; and f+h is 4. Inan embodiment, the halogenating agent is TiCl₄. In a further embodiment,the halogenation is conducted in the presence of a chlorinated or anon-chlorinated aromatic liquid, such as dichlorobenzene,o-chlorotoluene, chlorobenzene, benzene, toluene, or xylene. In yetanother embodiment, the halogenation is conducted by use of a mixture ofhalogenating agent and chlorinated aromatic liquid comprising from 40 to60 volume percent halogenating agent, such as TiCl₄.

In an embodiment, the reaction mixture is heated during halogenation.The procatalyst precursor and halogenating agent are contacted initiallyat a temperature from 0° C. to 60° C., or from 20° C. to 30° C., or from60° C. to 130° C., and heating is commenced at a rate of 0.1 to 10.0°C./minute, or at a rate of 1.0 to 5.0° C./minute. The internal electrondonor may be added later, after an initial contact period between thehalogenating agent and procatalyst precursor. Temperatures for thehalogenation are from 60° C. to 150° C. (or any value or subrangetherebetween), or from 90° C. to 120° C. Halogenation may be continuedin the substantial absence of the internal electron donor for a periodfrom 5 to 60 minutes, or from 10 to 50 minutes.

The manner in which the procatalyst precursor, the halogenating agentand the internal electron donor are contacted may be varied. In anembodiment, the procatalyst precursor is first contacted with a mixturecontaining the halogenating agent and a chlorinated aromatic compound.The resulting mixture is stirred and may be heated if desired. Next, theinternal electron donor is added to the same reaction mixture withoutisolating or recovering of the precursor. The foregoing process may beconducted in a single reactor with addition of the various ingredientscontrolled by automated process control.

In an embodiment, the procatalyst precursor is contacted with theinternal electron donor before reacting with halogenating agent.

Contact times of the procatalyst precursor with the internal electrondonor are at least 10 minutes, or at least 15 minutes, or at least 20minutes, or at least 1 hour at a temperature from at least 25° C., or atleast 50° C., or at least 60° C. up to a temperature of 150° C., or upto 120° C., or up to 115° C., or up to 110° C.

In an embodiment, the procatalyst precursor, the internal electrondonor, and the halogenating agent are added simultaneously orsubstantially simultaneously.

The halogenation procedure may be repeated one, two, three, or moretimes as desired. In an embodiment, the resulting solid material isrecovered from the reaction mixture and contacted one or more times inthe absence (or in the presence) of the same (or different) internalelectron donor components with a mixture of the halogenating agent inthe chlorinated aromatic compound for at least about 10 minutes, or atleast about 15 minutes, or at least about 20 minutes, and up to about 10hours, or up to about 45 minutes, or up to about 30 minutes, at atemperature from at least about 25° C., or at least about 50° C., or atleast about 60° C., to a temperature up to about 150° C., or up to about120° C., or up to about 115° C.

After the foregoing halogenation procedure, the resulting solidprocatalyst composition is separated from the reaction medium employedin the final process, by filtering for example, to produce a moistfilter cake. The moist filter cake may then be rinsed or washed with aliquid diluent to remove unreacted TiCl₄ and may be dried to removeresidual liquid, if desired. Typically the resultant solid procatalystcomposition is washed one or more times with a “wash liquid,” which is aliquid hydrocarbon such as an aliphatic hydrocarbon such as isopentane,isooctane, isohexane, hexane, pentane, or octane. The solid procatalystcomposition then can be separated and dried or slurried in ahydrocarbon, especially a relatively heavy hydrocarbon such as mineraloil for further storage or use.

In an embodiment, the resulting solid procatalyst composition has atitanium content of from about 1.0 percent by weight to about 6.0percent by weight, based on the total solids weight, or from about 1.5percent by weight to about 4.5 percent by weight, or from about 2.0percent by weight to about 3.5 percent by weight. The weight ratio oftitanium to magnesium in the solid procatalyst composition is suitablybetween about 1:3 and about 1:160, or between about 1:4 and about 1:50,or between about 1:6 and 1:30. In an embodiment, the internal electrondonor may be present in the procatalyst composition in a molar ratio ofinternal electron donor to magnesium of from about 0.005:1 to about 1:1,or from about 0.01:1 to about 0.4:1. Weight percent is based on thetotal weight of the procatalyst composition.

In an embodiment, the procatalyst composition may be further treated byone or more of the following procedures prior to or after isolation ofthe solid procatalyst composition. The solid procatalyst composition maybe contacted (halogenated) with a further quantity of titanium halidecompound, if desired; it may be exchanged under metathesis conditionswith an acid chloride, such as phthaloyl dichloride or benzoyl chloride;and it may be rinsed or washed, heat treated; or aged. The foregoingadditional procedures may be combined in any order or employedseparately, or not at all.

Not wishing to be bound by any particular theory, it is believed that(1) further halogenation by contacting the previously formed procatalystcomposition with a titanium halide compound, especially a solutionthereof in a halohydrocarbon diluent, and/or (2) further washing thepreviously formed procatalyst composition with a halohydrocarbon at anelevated temperature (100-150° C.), results in desirable modification ofthe procatalyst composition, possibly by removal of certain inactive orundesired metal compounds that are soluble in the foregoing diluent.Accordingly, in an embodiment, the procatalyst is contacted with ahalogenating agent, such as a mixture of a titanium halide and ahalohydrocarbon diluent, such as TiCl₄ and chlorobenzene, one or moretimes prior to isolation or recovery. In another embodiment, theprocatalyst is washed at a temperature between 100 to 150° C. withchlorobenzene or o-chlorotoluene one or more times prior to isolation orrecovery.

The present process for producing a procatalyst composition may comprisetwo or more embodiments disclosed herein.

In an embodiment, a procatalyst composition is provided which includes acombination of a magnesium moiety, a titanium moiety and an internalelectron donor. The internal electron donor includes the substitutedphenylene aromatic diester. The procatalyst composition is produced byway of the foregoing halogenation procedure which converts theprocatalyst precursor and the substituted phenylene aromatic diesterdonor into the combination of the magnesium and titanium moieties, intowhich the internal electron donor is incorporated. The procatalystprecursor from which the procatalyst composition is formed can be themagnesium moiety precursor, the mixed magnesium/titanium precursor, orthe benzoate-containing magnesium chloride precursor.

In an embodiment, the magnesium moiety is a magnesium halide. In anotherembodiment, the magnesium halide is magnesium chloride, or magnesiumchloride alcohol adduct.

In an embodiment, the titanium moiety is a titanium halide such as atitanium chloride. In another embodiment the titanium moiety is titaniumtetrachloride.

In another embodiment, the procatalyst composition includes a magnesiumchloride support upon which a titanium chloride is deposited and uponwhich the internal electron donor is incorporated.

In an embodiment, the internal electron donor of the procatalystcomposition includes the substituted phenylene aromatic diester ofstructure (I):

wherein R₁-R₁₄ are the same or different. Each of R₁-R₁₄ is selectedfrom hydrogen, a substituted hydrocarbyl group having 1 to 20 carbonatoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms,an alkoxy group having 1 to 20 carbon atoms, a heteroatom, andcombinations thereof. At least one of R₁-R₁₄ is not hydrogen.

In an embodiment, the substituted phenylene aromatic diester may be anysubstituted phenylene aromatic diester as disclosed in U.S. patentapplication Ser. No. 61/141,959 filed on Dec. 31, 2008 (Docket No.68188), the entire content of which is incorporated by reference herein.

In an embodiment, at least one (or two, or three, or four) R group(s) ofR₁-R₄ is selected from a substituted hydrocarbyl group having 1 to 20carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20 carbonatoms, an alkoxy group having 1 to 20 carbon atoms, a heteroatom, andcombinations thereof.

In an embodiment, at least one (or some, or all) R group(s) of R₅-R₁₄ isselected from a substituted hydrocarbyl group having 1 to 20 carbonatoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms,an alkoxy group having 1 to 20 carbon atoms, a heteroatom, andcombinations thereof. In another embodiment, at least one of R₅-R₉ andat least one of R₁₀-R₁₄ is selected from a substituted hydrocarbyl grouphaving 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group having 1to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, aheteroatom, and combinations thereof.

In an embodiment, at least one of R₁-R₄ and at least one of R₅-R₁₄ isselected from a substituted hydrocarbyl group having 1 to 20 carbonatoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms,an alkoxy group having 1 to 20 carbon atoms, a heteroatom, andcombinations thereof. In another embodiment, at least one of R₁-R₄ atleast one R₅-R₉ of and at least one of R₁₀-R₁₄ is selected from asubstituted hydrocarbyl group having 1 to 20 carbon atoms, anunsubstituted hydrocarbyl group having 1 to 20 carbon atoms, an alkoxygroup having 1 to 20 carbon atoms, a heteroatom, and combinationsthereof.

In an embodiment, any consecutive R groups in R₁-R₄, and/or anyconsecutive R groups in R₅-R₉, and/or any consecutive R groups inR₁₀-R₁₄ may be linked to form an inter-cyclic or an intra-cyclicstructure. The inter-/intra-cyclic structure may or may not be aromatic.In an embodiment, the inter-/intra-cyclic structure is a C₅ or a C₆membered ring.

In an embodiment, at least one of R₁-R₄ is selected from a substitutedhydrocarbyl group having 1 to 20 carbon atoms, an unsubstitutedhydrocarbyl group having 1 to 20 carbon atoms, and combinations thereof.Optionally, at least one of R₅-R₁₄ may be a halogen atom or an alkoxygroup having 1 to 20 carbon atoms. Optionally, R₁-R₄, and/or R₅-R₉,and/or R₁₀-R₁₄ may be linked to form an inter-cyclic structure or anintra-cyclic structure. The inter-cyclic structure and/or theintra-cyclic structure may or may not be aromatic.

In an embodiment, any consecutive R groups in R₁-R₄, and/or in R₅-R₉,and/or in R₁₀-R₁₄, may be members of a C₅-C₆-membered ring.

In an embodiment, structure (I) includes R₁, R₃ and R₄ as hydrogen. R₂is selected from a substituted hydrocarbyl group having 1 to 20 carbonatoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms,and combinations thereof. R₅-R₁₄ are the same or different and each ofR₅-R₁₄ is selected from hydrogen, a substituted hydrocarbyl group having1 to 20 carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen,and combinations thereof.

In an embodiment, R₂ is selected from a C₁-C₈ alkyl group, a C₃-C₆cycloalkyl, or a substituted C₃-C₆ cycloalkyl group. R₂ can be a methylgroup, an ethyl group, a n-propyl group, an isopropyl group, a t-butylgroup, an isobutyl group, a sec-butyl group, a2,4,4-trimethylpentan-2-yl group, a cyclopentyl group, and a cyclohexylgroup.

In an embodiment, structure (I) includes R₂ that is methyl, and each ofR₅-R₁₄ is hydrogen.

In an embodiment, structure (I) includes R₂ that is ethyl, and each ofR₅-R₁₄ is hydrogen.

In an embodiment, structure (I) includes R₂ that is t-butyl, and each ofR₅-R₁₄ is hydrogen.

In an embodiment, structure (I) includes R₂ that is ethoxycarbonyl, andeach of R₅-R₁₄ is hydrogen.

In an embodiment, structure (I) includes R₂, R₃ and R₄ each as hydrogenand R₁ is selected from a substituted hydrocarbyl group having 1 to 20carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20 carbonatoms, and combinations thereof. R₅-R₁₄ are the same or different andeach is selected from hydrogen, a substituted hydrocarbyl group having 1to 20 carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen,and combinations thereof.

In an embodiment, structure (I) includes R₁ that is methyl, and each ofR₅-R₁₄ is hydrogen.

In an embodiment, structure (I) includes R₂ and R₄ that are hydrogen andR₁ and R₃ are the same or different. Each of R₁ and R₃ is selected froma substituted hydrocarbyl group having 1 to 20 carbon atoms, anunsubstituted hydrocarbyl group having 1 to 20 carbon atoms, andcombinations thereof. R₅-R₁₄ are the same or different and each ofR₅-R₁₄ is selected from a substituted hydrocarbyl group having 1 to 20carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20 carbonatoms, an alkoxy group having 1 to 20 carbon atoms, a halogen, andcombinations thereof.

In an embodiment, structure (I) includes R₁ and R₃ that are the same ordifferent. Each of R₁ and R₃ is selected from a C₁-C₈ alkyl group, aC₃-C₆ cycloalkyl group, or a substituted C₃-C₆ cycloalkyl group. R₅-R₁₄are the same or different and each of R₅-R₁₄ is selected from hydrogen,a C₁-C₈ alkyl group, and a halogen. Nonlimiting examples of suitableC₁-C₈ alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl,i-butyl, t-butyl, n-pentyl, i-pentyl, neopentyl, t-pentyl, n-hexyl, and2,4,4-trimethylpentan-2-yl group. Nonlimiting examples of suitable C₃-C₆cycloalkyl groups include cyclopentyl and cyclohexyl groups. In afurther embodiment, at least one of R₅-R₁₄ is a C₁-C₈ alkyl group or ahalogen.

In an embodiment, structure (I) includes R₁ that is a methyl group andR₃ that is a t-butyl group. Each of R₂, R₄ and R₅-R₁₄ is hydrogen.

In an embodiment, structure (I) includes R₁ and R₃ that is an isopropylgroup. Each of R₂, R₄ and R₅-R₁₄ is hydrogen.

In an embodiment, structure (I) includes each of R₁, R₅, and R₁₀ as amethyl group and R₃ is a t-butyl group. Each of R₂, R₄, R₆-R₉ andR₁₁-R₁₄ is hydrogen.

In an embodiment, structure (I) includes each of R₁, R₇, and R₁₂ as amethyl group and R₃ is a t-butyl group. Each of R₂, R₄, R₅, R₆, R₈, R₉,R₁₀, R₁₁, R₁₃, and R₁₄ is hydrogen.

In an embodiment, structure (I) includes R₁ as a methyl group and R₃ isa t-butyl group. Each of R₇ and R₁₂ is an ethyl group. Each of R₂, R₄,R₅, R₆, R₈, R₉, R₁₀, R₁₁, R₁₃, and R₁₄ is hydrogen.

In an embodiment, structure (I) includes each of R₁, R₅, R₇, R₉, R₁₀,R₁₂, and R₁₄ as a methyl group and R₃ is a t-butyl group. Each of R₂,R₄, R₆, R₈, R₁₁, and R₁₃ is hydrogen.

In an embodiment, structure (I) includes R₁ as a methyl group and R₃ isa t-butyl group. Each of R₅, R₇, R₉, R₁₀, R₁₂, and R₁₄ is an i-propylgroup. Each of R₂, R₄, R₆, R₈, R₁₁, and R₁₃ is hydrogen.

In an embodiment, the substituted phenylene aromatic diester has astructure (II) which includes R₁ that is a methyl group and R₃ is at-butyl group. Each of R₂ and R₄ is hydrogen. R₈ and R₉ are members of aC₆ membered ring to form a 1-naphthoyl moiety. R₁₃ and R₁₄ are membersof a C₆ membered ring to form another 1-naphthoyl moiety. Structure (II)is provided below.

In an embodiment, the substituted phenylene aromatic diester has astructure (III) which includes R₁ that is a methyl group and R₃ is at-butyl group. Each of R₂ and R₄ is hydrogen. R₆ and R₇ are members of aC₆ membered ring to form a 2-naphthoyl moiety. R₁₂ and R₁₃ are membersof a C₆ membered ring to form a 2-naphthoyl moiety. Structure (III) isprovided below.

In an embodiment, structure (I) includes R₁ that is a methyl group andR₃ is a t-butyl group. Each of R₇ and R₁₂ is an ethoxy group. Each ofR₂, R₄, R₅, R₆, R₈, R₉, R₁₀, R₁₁, R₁₃, and R₁₄ is hydrogen.

In an embodiment, structure (I) includes R₁ that is a methyl group andR₃ is a t-butyl group. Each of R₇ and R₁₂ is a fluorine atom. Each ofR₂, R₄, R₅, R₆, R₈, R₉, R₁₀, R₁₁, R₁₃, and R₁₄ is hydrogen.

In an embodiment, structure (I) includes R₁ that is a methyl group andR₃ is a t-butyl group. Each of R₇ and R₁₂ is a chlorine atom. Each ofR₂, R₄, R₅, R₆, R₈, R₉, R₁₀, R₁₁, R₁₃, and R₁₄ is hydrogen.

In an embodiment, structure (I) includes R₁ that is a methyl group andR₃ is a t-butyl group. Each of R₇ and R₁₂ is a bromine atom. Each of R₂,R₄, R₅, R₆, R₈, R₉, R₁₀, R₁₁, R₁₃, and R₁₄ is hydrogen.

In an embodiment, structure (I) includes R₁ that is a methyl group andR₃ is a t-butyl group. Each of R₇ and R₁₂ is an iodine atom. Each of R₂,R₄, R₅, R₆, R₈, R₉, R₁₀, R₁₁, R₁₃, and R₁₄ is hydrogen.

In an embodiment, structure (I) includes R₁ that is a methyl group andR₃ is a t-butyl group. Each of R₆, R₇, R₁₁, and R₁₂ is a chlorine atom.Each of R₂, R₄, R₅, R₈, R₉, R₁₀, R₁₃, and R₁₄ is hydrogen.

In an embodiment, structure (I) includes R₁ that is a methyl group andR₃ is a t-butyl group. Each of R₆, R₈, R₁₁, and R₁₃ is a chlorine atom.Each of R₂, R₄, R₅, R₇, R₉, R₁₀, R₁₂, and R₁₄ is hydrogen.

In an embodiment, structure (I) include R₁ that is a methyl group and R₃is a t-butyl group. Each of R₂, R₄ and R₅-R₁₄ is a fluorine atom.

In an embodiment, structure (I) includes R₁ that is a methyl group andR₃ is a t-butyl group. Each of R₇ and R₁₂ is a trifluoromethyl group.Each of R₂, R₄, R₅, R₆, R₈, R₉, R₁₀, R₁₁, R₁₃, and R₁₄ is hydrogen.

In an embodiment, structure (I) includes R₁ that is a methyl group andR₃ is a t-butyl group. Each of R₇ and R₁₂ is an ethoxycarbonyl group.Each of R₂, R₄, R₅, R₆, R₈, R₉, R₁₀, R₁₁, R₁₃, and R₁₄ is hydrogen.

In an embodiment, R₁ is methyl group and R₃ is a t-butyl group. Each ofR₇ and R₁₂ is an ethoxy group. Each of R₂, R₄, R₅, R₆, R₈, R₉, R₁₀, R₁₁,R₁₃, and R₁₄ is hydrogen.

In an embodiment, structure (I) includes R₁ that is a methyl group andR₃ is a t-butyl group. Each of R₇ and R₁₂ is an diethylamino group. Eachof R₂, R₄, R₅, R₆, R₈, R₉, R₁₀, R₁₁, R₁₃, and R₁₄ is hydrogen.

In an embodiment, structure (I) includes R₁ that is a methyl group andR₃ is a 2,4,4-trimethylpentan-2-yl group. Each of R₂, R₄ and R₅-R₁₄ ishydrogen.

In an embodiment, structure (I) includes R₁ and R₃, each of which is asec-butyl group. Each of R₂, R₄ and R₅-R₁₄ is hydrogen.

In an embodiment, the substituted phenylene aromatic diester has astructure (IV) whereby R₁ and R₂ are members of a C₆ membered ring toform a 1,2-naphthalene moiety. Each of R₅-R₁₄ is hydrogen. Structure(IV) is provided below.

In an embodiment, the substituted phenylene aromatic diester has astructure (V) whereby R₂ and R₃ are members of a C₆ membered ring toform a 2,3-naphthalene moiety. Each of R₅-R₁₄ is hydrogen. Structure (V)is provided below.

In an embodiment, structure (I) includes R₁ and R₄ that are each amethyl group. Each of R₂, R₃, R₅-R₉ and R₁₀-R₁₄ is hydrogen.

In an embodiment, structure (I) includes R₁ that is a methyl group. R₄is an i-propyl group. Each of R₂, R₃, R₅-R₉ and R₁₀-R₁₄ is hydrogen.

In an embodiment, structure (I) includes R₁, R₃, and R₄, each of whichis an i-propyl group. Each of R₂, R₅-R₉ and R₁₀-R₁₄ is hydrogen.

Ethoxide content in the procatalyst composition indicates thecompleteness of conversion of precursor metal ethoxide into a metalhalide. The present internal electron donor assists in convertingethoxide into halide during halogenation. In an embodiment, theprocatalyst composition includes from about 0.01 wt % to about 1.0 wt %,or from about 0.05 wt % to about 0.5 wt % ethoxide. Weight percent isbased on the total weight of the procatalyst composition.

In an embodiment, the procatalyst composition includes from about 0.1 wt% to about 30.0 wt %, or from about 1.0 wt % to about 25.0 wt %, or fromabout 5.0 wt % to about 20.0 wt % substituted phenylene aromaticdiester. Weight percent is based on the total weight of the procatalystcomposition.

In an embodiment, the procatalyst composition includes from about 0.1 wt% to about 6.0 wt %, or from about 1.0 wt % to about 5.0 wt % titanium.Weight percent is based on the total weight of the procatalystcomposition.

In an embodiment, the magnesium to internal electron donor molar ratiois from about 100:1 to about 1:1, or from about 30:1 to about 2:1, orfrom about 20:1 to about 3:1.

In an embodiment, another procatalyst composition is provided. Theprocatalyst composition includes a combination of a magnesium moiety, atitanium moiety and a mixed internal electron donor. As used herein, a“mixed internal electron donor” is (i) a substituted phenylene aromaticdiester, (ii) an electron donor component that donates a pair ofelectrons to one or more metals present in the resultant procatalystcomposition, and (iii) optionally other components. In an embodiment,the electron donor component is a phthalate, a diether, a benzoate, andcombinations thereof. The procatalyst composition with the mixedinternal electron donor can be produced by way of the procatalystproduction procedure as previously disclosed.

The present procatalyst compositions may comprise two or moreembodiments disclosed herein.

In an embodiment, a catalyst composition is provided. As used herein, “acatalyst composition” is a composition that forms an olefin-basedpolymer when contacted with an olefin under polymerization conditions.The catalyst composition includes a procatalyst composition and acocatalyst. The procatalyst composition can be any of the foregoingprocatalyst compositions containing a substituted phenylene aromaticdiester. The catalyst composition may optionally include an externalelectron donor and/or an activity limiting agent.

In an embodiment, the internal electron donor of the catalystcomposition is a substituted phenylene aromatic diester. The substitutedphenylene aromatic diester can be any substituted phenylene aromaticdiester as disclosed herein.

In an embodiment, the internal electron donor of the catalystcomposition is a mixed internal electron donor. The mixed internalelectron donor can include (i) a substituted phenylene aromatic diesterand a phthalate, (ii) a substituted phenylene aromatic diester and abenzoate (such as ethyl benzoate), or (iii) a substituted phenylenearomatic diester and a diether.

The catalyst composition includes a cocatalyst. As used herein, a“cocatalyst” is a substance capable of converting the procatalyst to anactive polymerization catalyst. The cocatalyst may include hydrides,alkyls, or aryls of aluminum, lithium, zinc, tin, cadmium, beryllium,magnesium, and combinations thereof. In an embodiment, the cocatalyst isa hydrocarbyl aluminum cocatalyst represented by the formula R₃Alwherein each R is an alkyl, cycloalkyl, aryl, or hydride radical; atleast one R is a hydrocarbyl radical; two or three R radicals can bejoined in a cyclic radical forming a heterocyclic structure; each R canbe the same or different; and each R, which is a hydrocarbyl radical,has 1 to 20 carbon atoms, and preferably 1 to 10 carbon atoms. In afurther embodiment, each alkyl radical can be straight or branched chainand such hydrocarbyl radical can be a mixed radical, i.e., the radicalcan contain alkyl, aryl, and/or cycloalkyl groups. Nonlimiting examplesof suitable radicals are: methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2-methylpentyl,n-heptyl, n-octyl, isooctyl, 2-ethylhexyl, 5,5-dimethylhexyl, n-nonyl,n-decyl, isodecyl, n-undecyl, n-dodecyl.

Nonlimiting examples of suitable hydrocarbyl aluminum compounds are asfollows: triisobutylaluminum, tri-n-hexylaluminum, diisobutylaluminumhydride, di-n-hexylaluminum hydride, isobutylaluminum dihydride,n-hexylaluminum dihydride, diisobutylhexylaluminum,isobutyldihexylaluminum, trimethylaluminum, triethylaluminum,tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum,tri-n-octylaluminum, tri-n-decylaluminum, tri-n-dodecylaluminum. In anembodiment, the cocatalyst is selected from triethylaluminum,triisobutylaluminum, tri-n-hexylaluminum, diisobutylaluminum hydride,and di-n-hexylaluminum hydride.

In an embodiment, the cocatalyst is a hydrocarbyl aluminum compoundrepresented by the formula R_(n)AlX_(3-n) wherein n=1 or 2, R is analkyl, and X is a halide or alkoxide. Nonlimiting examples of suitablecompounds are as follows: methylaluminoxane, isobutylaluminoxane,diethylaluminum ethoxide, diisobutylaluminum chloride,tetraethyldialuminoxane, tetraisobutyldialuminoxane, diethylaluminumchloride, ethylaluminum dichloride, methylaluminum dichloride, anddimethylaluminum chloride.

In an embodiment, the cocatalyst is triethylaluminum. The molar ratio ofaluminum to titanium is from about 5:1 to about 500:1, or from about10:1 to about 200:1, or from about 15:1 to about 150:1, or from about20:1 to about 100:1. In another embodiment, the molar ratio of aluminumto titanium is about 45:1.

In an embodiment, the catalyst composition includes an external electrondonor. As used herein, an “external electron donor” is a compound addedindependent of procatalyst formation and contains at least onefunctional group that is capable of donating a pair of electrons to ametal atom. Bounded by no particular theory, it is believed that theexternal electron donor enhances catalyst stereoselectivity, (i.e., toreduces xylene soluble material in the formant polymer).

In an embodiment, the external electron donor may be selected from oneor more of the following: an alkoxysilane, an amine, an ether, acarboxylate, a ketone, an amide, a carbamate, a phosphine, a phosphate,a phosphite, a sulfonate, a sulfone, and/or a sulfoxide.

In an embodiment, the external electron donor is an alkoxysilane. Thealkoxysilane has the general formula: SiR_(m)(OR′)_(4-m) (I) where Rindependently each occurrence is hydrogen or a hydrocarbyl or an aminogroup optionally substituted with one or more substituents containingone or more Group 14, 15, 16, or 17 heteroatoms, said R containing up to20 atoms not counting hydrogen and halogen; R′ is a C₁₋₄ alkyl group;and m is 0, 1, 2 or 3. In an embodiment, R is C₆₋₁₂ aryl, alkyl oraralkyl, C₃₋₁₂ cycloalkyl, C₃₋₁₂ branched alkyl, or C₃₋₁₂ cyclic oracyclic amino group, R′ is C₁₋₄ alkyl, and m is 1 or 2. Nonlimitingexamples of suitable silane compositions includedicyclopentyldimethoxysilane, di-tert-butyldimethoxysilane,methylcyclohexyldimethoxysilane, methylcyclohexyldiethoxysilane,ethylcyclohexyldimethoxysilane, diphenyldimethoxysilane,diisopropyldimethoxysilane, di-n-propyldimethoxysilane,diisobutyldimethoxysilane, diisobutyldiethoxysilane,isobutylisopropyldimethoxysilane, di-n-butyldimethoxysilane,cyclopentyltrimethoxysilane, isopropyltrimethoxysilane,n-propyltrimethoxysilane, n-propyltriethoxysilane, ethyltriethoxysilane,tetramethoxysilane, tetraethoxysilane, diethylaminotriethoxysilane,cyclopentylpyrrolidinodimethoxysilane, bis(pyrrolidino)dimethoxysilane,bis(perhydroisoquinolino)dimethoxysilane, and dimethyldimethoxysilane.In an embodiment, the silane composition is dicyclopentyldimethoxysilane(DCPDMS), methylcyclohexyldimethoxysilane (MChDMS), orn-propyltrimethoxysilane (NPTMS), and any combination of thereof.

In an embodiment, the external donor can be a mixture of at least 2alkoxysilanes. In a further embodiment, the mixture can bedicyclopentyldimethoxysilane and methylcyclohexyldimethoxysilane,dicyclopentyldimethoxysilane and tetraethoxysilane, ordicyclopentyldimethoxysilane and n-propyltriethoxysilane.

In an embodiment, the external electron donor is selected from one ormore of the following: a benzoate, a succinate, and/or a diolester. Inan embodiment, the external electron donor is2,2,6,6-tetramethylpiperidine. In another embodiment, the externalelectron donor is a diether.

In an embodiment, the catalyst composition includes an activity limitingagent (ALA). As used herein, an “activity limiting agent” (“ALA”) is amaterial that reduces catalyst activity at elevated temperature (i.e.,temperature greater than about 85° C.). An ALA inhibits or otherwiseprevents polymerization reactor upset and ensures continuity of thepolymerization process. Typically, the activity of Ziegler-Nattacatalysts increases as the reactor temperature rises. Ziegler-Nattacatalysts also typically maintain high activity near the melting pointtemperature of the polymer produced. The heat generated by theexothermic polymerization reaction may cause polymer particles to formagglomerates and may ultimately lead to disruption of continuity for thepolymer production process. The ALA reduces catalyst activity atelevated temperature, thereby preventing reactor upset, reducing (orpreventing) particle agglomeration, and ensuring continuity of thepolymerization process.

The activity limiting agent may be a carboxylic acid ester, a diether, apoly(alkene glycol), poly(alkene glycol)ester, a diol ester, andcombinations thereof. The carboxylic acid ester can be an aliphatic oraromatic, mono-or poly-carboxylic acid ester. Nonlimiting examples ofsuitable monocarboxylic acid esters include ethyl and methyl benzoate,ethyl p-methoxybenzoate, methyl p-ethoxybenzoate, ethylp-ethoxybenzoate, ethyl acrylate, methyl methacrylate, ethyl acetate,ethyl p-chlorobenzoate, hexyl p-aminobenzoate, isopropyl naphthenate,n-amyl toluate, ethyl cyclohexanoate and propyl pivalate.

Nonlimiting examples of suitable polycarboxylic acid esters includedimethyl phthalate, diethyl phthalate, di-n-propyl phthalate,diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate,di-tert-butyl phthalate, diisoamyl phthalate, di-tert-amyl phthalate,dineopentyl phthalate, di-2-ethylhexyl phthalate, di-2-ethyldecylphthalate, diethyl terephthalate, dioctyl terephthalate, andbis[4-(vinyloxy)butyl]terephthalate.

The aliphatic carboxylic acid ester may be a C₄-C₃₀ aliphatic acidester, may be a mono- or a poly- (two or more) ester, may be straightchain or branched, may be saturated or unsaturated, and any combinationthereof. The C₄-C₃₀ aliphatic acid ester may also be substituted withone or more Group 14, 15 or 16 heteroatom containing substituents.Nonlimiting examples of suitable C₄-C₃₀ aliphatic acid esters includeC₁₋₂₀ alkyl esters of aliphatic C₄₋₃₀ monocarboxylic acids, C₁₋₂₀ alkylesters of aliphatic C₈₋₂₀ monocarboxylic acids, C₁₋₄ allyl mono- anddiesters of aliphatic C₄₋₂₀ monocarboxylic acids and dicarboxylic acids,C₁₋₄ alkyl esters of aliphatic C₈₋₂₀ monocarboxylic acids anddicarboxylic acids, and C₄₋₂₀ mono- or polycarboxylate derivatives ofC₂₋₁₀₀ (poly)glycols or C₂₋₁₀₀ (poly)glycol ethers. In a furtherembodiment, the C₄-C₃₀ aliphatic acid ester may be a laurate, amyristate, a palmitate, a stearate, an oleates, a sebacate,(poly)(alkylene glycol) mono- or diacetates, (poly)(alkylene glycol)mono- or di-myristates, (poly)(alkylene glycol) mono- or di-laurates,(poly)(alkylene glycol) mono- or di-oleates, glyceryl tri(acetate),glyceryl tri-ester of C₂₋₄₀ aliphatic carboxylic acids, and mixturesthereof. In a further embodiment, the C₄-C₃₀ aliphatic ester isisopropyl myristate or di-n-butyl sebacate.

In an embodiment, the activity limiting agent includes a diether. Thediether can be a 1,3-diether compound represented by the followingstructure (VI):

wherein R₁ to R₄ are independently of one another an alkyl, aryl oraralkyl group having up to 20 carbon atoms, which may optionally containa group 14, 15, 16, or 17 heteroatom, and R₁ and R₂ may be a hydrogenatom. The dialkylether may linear or branched, and may include one ormore of the following groups: alkyl, cycloaliphatic, aryl, alkylaryl orarylalkyl radicals with 1-18 carbon atoms, and hydrogen. R₁ and R₂ maybe linked to form a cyclic structure, such as cyclopentadiene orfluorene.

In an embodiment, the activity limiting agent includes a succinatecomposition having the following structure (VII):

wherein R and R′ may be the same or different, R and/or R′ including oneor more of the following groups: hydrogen, linear or branched alkyl,alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group, optionallycontaining heteroatoms. One or more ring structures can be formed viaone or both 2- and 3-position carbon atom.

In an embodiment, the activity limiting agent includes a diol ester asrepresented by the following structure (VIII):

wherein n is an integer from 1 to 5. R₁ and R₂, may be the same ordifferent, and each may be selected from hydrogen, methyl, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, allyl, phenyl, orhalophenyl group. R₃, R₄, R₅, R₆, R₇, and R₈ may be the same ordifferent, and each may be selected from hydrogen, halogen, substituted,or unsubstituted hydrocarbyl having 1 to 20 carbon atoms. R₁-R₆ groupsmay optionally contain one or more heteroatoms replacing carbon,hydrogen or both, the hetero-atom selected from nitrogen, oxygen,sulfur, silicon, phosphorus and a halogen. R₇ and R₈, may be the same ordifferent, and may be bonded to any carbon atom of the 2-, 3-, 4-, 5-,and 6-position of either phenyl ring.

In an embodiment, the external electron donor and/or activity limitingagent can be added into the reactor separately. In another embodiment,the external electron donor and the activity limiting agent can be mixedtogether in advance and then added into the reactor as a mixture. In themixture, more than one external electron donor or more than one activitylimiting agent can be used. In an embodiment, the mixture isdicyclopentyldimethoxysilane and isopropyl myristate,dicyclopentyldimethoxysilane and poly(ethylene glycol)laurate,dicyclopentyldimethoxysilane and isopropyl myristate and poly(ethyleneglycol)dioleate, methylcyclohexyldimethoxysilane and isopropylmyristate, n-propyltrimethoxysilane and isopropyl myristate,dimethyldimethoxysilane and methylcyclohexyldimethoxysilane andisopropyl myristate, dicyclopentyldimethoxysilane andn-propyltriethoxysilane and isopropyl myristate, anddicyclopentyldimethoxysilane and tetraethoxysilane and isopropylmyristate, and combinations thereof.

In an embodiment, the catalyst composition includes any of the foregoingexternal electron donors in combination with any of the foregoingactivity limiting agents.

The present catalyst composition may comprise two or more embodimentsdisclosed herein.

In an embodiment, a process for producing an olefin-based polymer isprovided. The process includes contacting an olefin with a catalystcomposition under polymerization conditions. The catalyst compositionincludes a substituted phenylene aromatic diester. The substitutedphenylene aromatic diester can be any substituted phenylene dibenzoateas disclosed herein. The process further includes forming anolefin-based polymer.

In an embodiment, the catalyst composition includes a procatalystcomposition and a cocatalyst. The procatalyst composition may be anyprocatalyst composition as disclosed herein. The procatalyst compositionmay include a substituted phenylene aromatic diester as the internalelectron donor or a mixed internal electron donor as disclosed herein.The cocatalyst may be any cocatalyst as disclosed herein. The catalystcomposition may optionally include an external electron donor and/or anactivity limiting agent as previously disclosed.

In an embodiment, the olefin-based polymer can be a propylene-basedolefin, an ethylene-based olefin, and combinations thereof. In anembodiment, the olefin-based polymer is a propylene-based polymer.

One or more olefin monomers can be introduced into a polymerizationreactor to react with the catalyst and to form a polymer, or a fluidizedbed of polymer particles. Nonlimiting examples of suitable olefinmonomers include ethylene, propylene, C₄₋₂₀ α-olefins, such as 1-butene,1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene,1-dodecene and the like; C₄₋₂₀ diolefins, such as 1,3-butadiene,1,3-pentadiene, norbornadiene, 5-ethylidene-2-norbornene (ENB) anddicyclopentadiene; C₈₋₄₀ vinyl aromatic compounds including styrene, o-,m-, and p-methylstyrene, divinylbenzene, vinylbiphenyl, vinylnapthalene;and halogen-substituted C₈₋₄₀ vinyl aromatic compounds such aschlorostyrene and fluorostyrene.

As used herein, “polymerization conditions” are temperature and pressureparameters within a polymerization reactor suitable for promotingpolymerization between the catalyst composition and an olefin to formthe desired polymer. The polymerization process may be a gas phase, aslurry, or a bulk polymerization process, operating in one, or more thanone, reactor.

In an embodiment, polymerization occurs by way of gas phasepolymerization. As used herein, “gas phase polymerization” is thepassage of an ascending fluidizing medium, the fluidizing mediumcontaining one or more monomers, in the presence of a catalyst through afluidized bed of polymer particles maintained in a fluidized state bythe fluidizing medium. “Fluidization,” “fluidized,” or “fluidizing” is agas-solid contacting process in which a bed of finely divided polymerparticles is lifted and agitated by a rising stream of gas. Fluidizationoccurs in a bed of particulates when an upward flow of fluid through theinterstices of the bed of particles attains a pressure differential andfrictional resistance increment exceeding particulate weight. Thus, a“fluidized bed” is a plurality of polymer particles suspended in afluidized state by a stream of a fluidizing medium. A “fluidizingmedium” is one or more olefin gases, optionally a carrier gas (such asH₂ or N₂) and optionally a liquid (such as a hydrocarbon) which ascendsthrough the gas-phase reactor.

A typical gas-phase polymerization reactor (or gas phase reactor)includes a vessel (i.e., the reactor), the fluidized bed, a distributionplate, inlet and outlet piping, a compressor, a cycle gas cooler or heatexchanger, and a product discharge system. The vessel includes areaction zone and a velocity reduction zone, each of which is locatedabove the distribution plate. The bed is located in the reaction zone.In an embodiment, the fluidizing medium includes propylene gas and atleast one other gas such as an olefin and/or a carrier gas such ashydrogen or nitrogen.

In an embodiment, the contacting occurs by way of feeding the catalystcomposition into a polymerization reactor and introducing the olefininto the polymerization reactor. In an embodiment, the cocatalyst can bemixed with the procatalyst composition (pre-mix) prior to theintroduction of the procatalyst composition into the polymerizationreactor. In another embodiment, cocatalyst is added to thepolymerization reactor independently of the procatalyst composition. Theindependent introduction of the cocatalyst into the polymerizationreactor can occur simultaneously, or substantially simultaneously, withthe procatalyst composition feed.

In an embodiment, the polymerization process may include apre-polymerization step. Pre-polymerization includes contacting a smallamount of the olefin with the procatalyst composition after theprocatalyst composition has been contacted with the co-catalyst and theselectivity determining agent and/or the activity limiting agent. Then,the resulting preactivated catalyst stream is introduced into thepolymerization reaction zone and contacted with the remainder of theolefin monomer to be polymerized, and optionally one or more of theexternal electron donor components. Pre-polymerization results in theprocatalyst composition being combined with the cocatalyst and theselectivity determining agent and/or the activity limiting agent, thecombination being dispersed in a matrix of the formant polymer.Optionally, additional quantities of the selectivity determining agentand/or the activity limiting agent may be added.

In an embodiment, the polymerization process may include apre-activation step. Pre-activation includes contacting the procatalystcomposition with the co-catalyst and the selectivity determining agentand/or the activity limiting agent. The resulting preactivated catalyststream is subsequently introduced into the polymerization reaction zoneand contacted with the olefin monomer to be polymerized, and optionallyone or more of the external electron donor components. Pre-activationresults in the procatalyst composition being combined with thecocatalyst and the selectivity determining agent and/or the activitylimiting agent. Optionally, additional quantities of the selectivitydetermining agent and/or the activity limiting agent may be added.

In an embodiment, the process includes mixing the external electrondonor (and optionally the activity limiting agent) with the procatalystcomposition. The external electron donor can be complexed with thecocatalyst and mixed with the procatalyst composition (pre-mix) prior tocontact between the catalyst composition and the olefin. In anotherembodiment, the external electron donor and/or the activity limitingagent can be added independently to the polymerization reactor. In anembodiment, the external electron donor is dicyclopentyldimethoxysilaneor n-propyltrimethoxysilane.

In another embodiment, the catalyst composition includesdicyclopentyldimethoxysilane or n-propyltrimethoxysilane and an activitylimiting agent such as isopropyl myristate.

In an embodiment, a polypropylene homopolymer is produced in a firstreactor. The content of the first reactor is subsequently transferred toa second reactor into which ethylene is introduced. This results inproduction of a propylene-ethylene copolymer in the second reactor.

In an embodiment, a polypropylene homopolymer is formed via introductionof propylene and any of the present procatalyst compositions,cocatalysts, external electron donors, and activity limiting agents inthe first reactor. The polypropylene homopolymer is introduced into thesecond reactor along with ethylene and optionally an external electrondonor and/or an activity limiting agent. The external electron donor andthe activity limiting agent may be the same as or different from therespective components used in the first reactor. This produces apropylene-ethylene copolymer in the second reactor.

In an embodiment, the olefin is propylene. The process includes forminga propylene-based polymer having a melt flow rate (MFR) from about 0.01g/10 min to about 800 g/10 min, or from about 0.1 g/10 min to about 200g/10 min, or from about 0.5 g/10 min to about 150 g/10 min. In a furtherembodiment, the propylene-based polymer is a polypropylene homopolymer.

In an embodiment, the olefin is propylene. The process includes forminga propylene-based polymer having a xylene solubles content from about0.5% to about 10%, or from about 1% to about 8%, or from about 1% toabout 4%. In a further embodiment, the propylene-based polymer is apolypropylene homopolymer.

In an embodiment, the olefin is propylene. The process includes forminga propylene-based polymer having a polydispersity index (PDI) from about4 to about 15, or from about 4 to about 10, or from about 4 to about 8.In a further embodiment, the propylene-based polymer is a polypropylenehomopolymer.

The present disclosure provides another process. In an embodiment, apolymerization process is provided and includes contacting propylene andethylene and/or 1-butene with a catalyst composition underpolymerization conditions. The catalyst composition may be any catalystcomposition disclosed herein containing a substituted phenylene aromaticdiester. The process includes forming a random propylene-basedinterpolymer having an MFR from about 0.01 g/10 min to about 200 g/10min, or from about 0.1 g/10 min to about 100 g/10 min, or from about 0.5g/10 min to about 70 g/10 min. The formant propylene-based interpolymerhas a xylene solubles content from about 0.5% to about 40%, or fromabout 1% to about 30%, or from about 1% to about 20%.

The formant propylene-based interpolymer has a weight percent comonomercontent relative to propylene of from about 0.001% to about 20%, or fromabout 0.01% to about 15%, or from about 0.1% to about 10%.

In an embodiment, the olefin-based polymer (i.e., propylene-basedpolymer) produced by any of the foregoing processes comprises asubstituted phenylene aromatic diester.

The present polymerization process may comprise two or more embodimentsdisclosed herein.

Not wishing to be bound by any particular theory, it is believed thatthe present catalyst compositions with substituted phenylene aromaticdiester internal electron donor yield olefin-based polymers with a broadmolecular weight distribution, high catalyst activity, and highstereoselectivity. Moreover, the present substituted phenylene aromaticdiester advantageously provides the present procatalyst composition(s),catalyst composition(s), and olefin-based polymer(s) the property ofbeing phthalate-free, or otherwise void or devoid of phthalate and/orderivatives thereof.

Definitions

All references to the Periodic Table of the Elements herein shall referto the Periodic Table of the Elements, published and copyrighted by CRCPress, Inc., 2003. Also, any references to a Group or Groups shall be tothe Groups or Groups reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups. Unless stated to thecontrary, implicit from the context, or customary in the art, all partsand percents are based on weight. For purposes of United States patentpractice, the contents of any patent, patent application, or publicationreferenced herein are hereby incorporated by reference in their entirety(or the equivalent US version thereof is so incorporated by reference),especially with respect to the disclosure of synthetic techniques,definitions (to the extent not inconsistent with any definitionsprovided herein) and general knowledge in the art.

The term “comprising,” and derivatives thereof, is not intended toexclude the presence of any additional component, step or procedure,whether or not the same is disclosed herein. In order to avoid anydoubt, all compositions claimed herein through use of the term“comprising” may include any additional additive, adjuvant, or compoundwhether polymeric or otherwise, unless stated to the contrary. Incontrast, the term, “consisting essentially of” excludes from the scopeof any succeeding recitation any other component, step or procedure,excepting those that are not essential to operability. The term“consisting of” excludes any component, step or procedure notspecifically delineated or listed. The term “or”, unless statedotherwise, refers to the listed members individually as well as in anycombination.

Any numerical range recited herein, includes all values from the lowervalue to the upper value, in increments of one unit, provided that thereis a separation of at least 2 units between any lower value and anyhigher value. As an example, if it is stated that the amount of acomponent, or a value of a compositional or a physical property, suchas, for example, amount of a blend component, softening temperature,melt index, etc., is between 1 and 100, it is intended that allindividual values, such as, 1, 2, 3, etc., and all subranges, such as, 1to 20, 55 to 70, 197 to 100, etc., are expressly enumerated in thisspecification. For values which are less than one, one unit isconsidered to be 0.0001, 0.001, 0.01 or 0.1, as appropriate. These areonly examples of what is specifically intended, and all possiblecombinations of numerical values between the lowest value and thehighest value enumerated, are to be considered to be expressly stated inthis application. In other words, any numerical range recited hereinincludes any value or subrange within the stated range. Numerical rangeshave been recited, as discussed herein, reference melt index, melt flowrate, and other properties.

The terms “blend” or “polymer blend,” as used herein, is a blend of twoor more polymers. Such a blend may or may not be miscible (not phaseseparated at molecular level). Such a blend may or may not be phaseseparated. Such a blend may or may not contain one or more domainconfigurations, as determined from transmission electron spectroscopy,light scattering, x-ray scattering, and other methods known in the art.

The term “composition,” as used herein, includes a mixture of materialswhich comprise the composition, as well as reaction products anddecomposition products formed from the materials of the composition.

The term “polymer” is a macromolecular compound prepared by polymerizingmonomers of the same or different type. “Polymer” includes homopolymers,copolymers, terpolymers, interpolymers, and so on. The term“interpolymer” means a polymer prepared by the polymerization of atleast two types of monomers or comonomers. It includes, but is notlimited to, copolymers (which usually refers to polymers prepared fromtwo different types of monomers or comonomers, terpolymers (whichusually refers to polymers prepared from three different types ofmonomers or comonomers), tetrapolymers (which usually refers to polymersprepared from four different types of monomers or comonomers), and thelike.

The term “interpolymer,” as used herein, refers to polymers prepared bythe polymerization of at least two different types of monomers. Thegeneric term interpolymer thus includes copolymers, usually employed torefer to polymers prepared from two different monomers, and polymersprepared from more than two different types of monomers.

The term “olefin-based polymer” is a polymer containing, in polymerizedform, a majority weight percent of an olefin, for example ethylene orpropylene, based on the total weight of the polymer. Nonlimitingexamples of olefin-based polymers include ethylene-based polymers andpropylene-based polymers.

The term, “ethylene-based polymer,” as used herein, refers to a polymerthat comprises a majority weight percent polymerized ethylene monomer(based on the total weight of polymerizable monomers), and optionallymay comprise at least one polymerized comonomer.

The term, “ethylene/α-olefin interpolymer,” as used herein, refers to aninterpolymer that comprises a majority weight percent polymerizedethylene monomer (based on the total amount of polymerizable monomers),and at least one polymerized α-olefin.

The term, “propylene-based polymer,” as used herein, refers to a polymerthat comprises a majority weight percent polymerized propylene monomer(based on the total amount of polymerizable monomers), and optionallymay comprise at least one polymerized comonomer.

The term “alkyl,” as used herein, refers to a branched or unbranched,saturated or unsaturated acyclic hydrocarbon radical. Nonlimitingexamples of suitable alkyl radicals include, for example, methyl, ethyl,n-propyl, i-propyl, n-butyl, t-butyl, i-butyl (or 2-methylpropyl), etc.The alkyls have 1 and 20 carbon atoms.

The term “substituted alkyl,” as used herein, refers to an alkyl as justdescribed in which one or more hydrogen atom bound to any carbon of thealkyl is replaced by another group such as a halogen, aryl, substitutedaryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, halogen, haloalkyl, hydroxy, amino, phosphido, alkoxy,amino, thio, nitro, and combinations thereof. Suitable substitutedalkyls include, for example, benzyl, trifluoromethyl and the like.

The term “aryl,” as used herein, refers to an aromatic substituent whichmay be a single aromatic ring or multiple aromatic rings which are fusedtogether, linked covalently, or linked to a common group such as amethylene or ethylene moiety. The aromatic ring(s) may include phenyl,naphthyl, anthracenyl, and biphenyl, among others. The aryls have 1 and20 carbon atoms.

Test Methods

Flexural modulus is determined in accordance with ASTM D790-00.

Melt flow rate is measured in accordance with ASTM D 1238-01 test methodat 230° with a 2.16 kg weight for propylene-based polymers.

Xylene Solubles (XS) is measured using a ¹H NMR method as described inU.S. Pat. No. 5,539,309, the entire content of which is incorporatedherein by reference.

Polydispersity Index (PDI) is measured by an AR-G2 rheometer which is astress control dynamic spectrometer manufactured by TA Instruments usinga method according to Zeichner G R, Patel P D (1981) “A comprehensiveStudy of Polypropylene Melt Rheology” Proc. Of the 2^(nd) World Congressof Chemical Eng., Montreal, Canada. An ETC oven is used to control thetemperature at 180° C.±0.1° C. Nitrogen is used to purge the inside theoven to keep the sample from degradation by oxygen and moisture. A pairof 25 mm in diameter cone and plate sample holder is used. Samples arecompress molded into 50 mm×100 mm×2 mm plaque. Samples are then cut into19 mm square and loaded on the center of the bottom plate. Thegeometries of upper cone is (1) Cone angle: 5:42:20 (deg:min:I); (2)Diameter: 25 mm; (3) Truncation gap: 149 micron. The geometry of thebottom plate is 25 mm cylinder.

Testing procedure:

-   -   (1) The cone & plate sample holder are heated in the ETC oven at        180° C. for 2 hours. Then the gap is zeroed under blanket of        nitrogen gas.    -   (2) Cone is raised to 2.5 mm and sample loaded unto the top of        the bottom plate.    -   (3) Start timing for 2 minutes.    -   (4) The upper cone is immediately lowered to slightly rest on        top of the sample by observing the normal force.    -   (5) After two minutes the sample is squeezed down to 165 micron        gap by lower the upper cone.    -   (6) The normal force is observed. When the normal force is down        to <0.05 Newton the excess sample is removed from the edge of        the cone and plate sample holder by a spatula.    -   (7) The upper cone is lowered again to the truncation gap which        is 149 micron.    -   (8) An Oscillatory Frequency Sweep test is performed under these        conditions:        -   Test delayed at 180° C. for 5 minutes.        -   Frequencies: 628.3 r/s to 0.1 r/s.        -   Data acquisition rate: 5 point/decade.        -   Strain: 10%    -   (9) When the test is completed the crossover modulus (Gc) is        detected by the Rheology Advantage Data Analysis program        furnished by TA Instruments.    -   (10) PDI=100,000÷Gc (in Pa units).

Final melting point Tm(f) is the temperature to melt the most perfectcrystal in the sample and is regarded as a measure for isotacticity andinherent polymer crystallizability. The test was conducted using a TAQ100 Differential Scanning calorimeter. A sample is heated from 0° C. to240° C. at a rate of 80° C./min, cooled at the same rate to 0° C., thenheated again at the same rate up to 150° C., held at 150° C. for 5minutes and the heated from 150° C. to 180° C. at 1.25° C./min. TheTm(f) is determined from this last cycle by calculating the onset of thebaseline at the end of the heating curve.

Testing procedure:

-   -   (1) Calibrate instrument with high purity indium as standard.    -   (2) Purge the instrument head/cell with a constant 50 ml/min        flow rate of nitrogen constantly.    -   (3) Sample preparation:        -   Compression mold 1.5 g of powder sample using a            30-G302H-18-CX Wabash Compression Molder (30 ton): (a) heat            mixture at 230° C. for 2 minutes at contact; (b) compress            the sample at the same temperature with 20 ton pressure for            1 minute; (c) cool the sample to 45° F. and hold for 2            minutes with 20 ton pressure; (d) cut the plaque into 4 of            about the same size, stack them together, and repeat steps            (a)-(c) in order to homogenize sample.    -   (4) Weigh a piece of sample (preferably between 5 to 8 mg) from        the sample plaque and seal it in a standard aluminum sample pan.        Place the sealed pan containing the sample on the sample side of        the instrument head/cell and place an empty sealed pan in the        reference side. If using the auto sampler, weigh out several        different sample specimens and set up the machine for a        sequence.    -   (5) Measurements:        -   (i) Data storage: off        -   (ii) Ramp 80.00° C./min to 240.00° C.        -   (iii) Isothermal for 1.00 min        -   (iv) Ramp 80.00° C./min to 0.00° C.        -   (v) Isothermal for 1.00 min        -   (vi) Ramp 80.00° C./min to 150.00° C.        -   (vii) Isothermal for 5.00 min        -   (viii) Data storage: on        -   (ix) Ramp 1.25° C./min to 180.00° C.        -   (x) End of method    -   (6) Calculation: Tm(f) is determined by the interception of two        lines. Draw one line from the base-line of high temperature.        Draw another line from through the deflection of the curve close        to the end of the curve at high temperature side.

By way of example and not by limitation, examples of the presentdisclosure will now be provided.

I. Substituted Phenylene Aromatic Diester.

Substituted phenylene aromatic diester may be synthesized in accordancewith U.S. patent application Ser. No. 61/141,959 (Docket No. 68188)filed on Dec. 31, 2008, the entire content of which is incorporated byreference herein. Nonlimiting examples of suitable substituted phenylenearomatic diester are provided in Table 1 below.

TABLE 1 ¹H NMR (500 MHz, Compound Structure CDCl₃, ppm) 1,2-phenylenedibenzoate (IED1)*

δ 8.08 (dd, 4H), 7.54 (tt, 2H), 7.34-7.43 (m, 8H).3-methyl-5-tert-butyl-1,2- phenylene dibenzoate (IED2)

δ 8.08 (dd, 2H), 8.03 (dd, 2H), 7.53 (tt, 1H), 7.50 (tt, 1H), 7.38 (t,2H), 7.34 (t, 2H), 7.21 (d, 1H), 7.19 (d, 1H), 2.28 (s, 3H), 1.34 (s,9H). 3,5-diisopropyl-1,2-phenylene dibenzoate (IED3)

δ 8.08 (dd, 2H), 7.00 (dd, 2H), 7.53 (tt, 1H), 7.48 (tt, 1H), 7.39 (t,2H), 7.31 (t, 2H), 7.11 (d, 1H), 7.09 (d, 1H), 3.11 (heptat, 1H), 2.96(heptat, 1H), 1.30 (d, 6H), 1.26 (d, 6H). 3,6-dimethyl-1,2-phenylenedibenzoate (IED4)

δ 8.08 (d, 2H), 7.51 (t, 1H), 7.34 (d, 2H), 7.11 (s, 2H), 2.23 (s, 6H).4-t-butyl-1,2-phenylene dibenzoate (IED5)

δ 8.07 (dd, 4H), 7.54 (m, 2H), 7.30-7.40 (m, 7H), 1.37 (s, 9H). 4-methyl1,2-phenylene dibenzoate (IED6)

δ (ppm) 8.07 (d, 4H), 7.54 (t, 2H), 7.37 (t, 4H), 7.27 (d, 1H), 7.21 (s,1H), 7.15 (d, 1H), 2.42 (s, 3H). 1,2-naphthalene dibenzoate (IED7)

δ 8.21-8.24 (m, 2H), 8.08-8.12 (m, 2H), 7.90- 7.96 (m, 2H), 7.86 (d,1H), 7.60 (m, 1H), 7.50- 7.55 (m ,4H), 7.46 (t, 2H), 7.37 (t, 2H).2,3-naphthalene dibenzoate (IED8)

δ 8.08-8.12 (m, 4H), 7.86-7.90 (m, 4H), 7.51- 7.58 (m, 4H), 7.38 (t, 4H)1,2-phenylene dibenzoate (IED1)*

δ 8.08 (dd, 4H), 7.54 (tt, 2H), 7.34-7.43 (m, 8H).3-methyl-5-tert-butyl-1,2- phenylene dibenozate (IED2)

δ 8.08 (dd, 2H), 8.03 (dd, 2H), 7.53 (tt, 1H), 7.50 (tt, 1H), 7.38 (t,2H), 7.34 (t, 2H), 7.21 (d, 1H), 7.19 (d, 1H), 2.28 (s, 3H), 1.34 (s,9H). 3,5-diisopropyl-1,2-phenylene dibenzoate (IED3)

δ 8.08 (dd, 2H), 7.00 (dd, 2H), 7.53 (tt, 1H), 7.48 (tt, 1H), 7.39 (t,2H), 7.31 (t, 2H), 7.11 (d, 1H), 7.09 (d, 1H), 3.11 (heptat, 1H), 2.96(heptat, 1H), 1.30 (d, 6H), 1.26 (d, 6H). 3-methyl-5-tert-butyl-1,2-phenylene di(4-methylbenzoate) (IED9)

δ (ppm) 7.98 (d, 2H), 7.93 (d, 2H), 7.18 (d, 4H), 7.15 (d, 2H), 2.38 (s,3H), 2.36 (s, 3H), 2.26 (s, 3H), 1.35 (s, 9H).3-methyl-5-tert-butyl-1,2- phenylene di(2,4,6- trimethylbenzoate)(IED10)

δ (ppm) 7.25 (s, 1H), 7.21 (s, 1H), 6.81 (d, 4H), 2.36 (s, 3H), 2.30 (d,6H), 2.25 (s, 6H), 2.23 (s, 6H), 1.36 (s, 9H).3-methyl-5-tert-butyl-1,2- phenylene di(4-fluorobenzoate) (IED11)

δ 7.98 (dd, 4H), 7.36 (dd, 4H), 7.21 (s, 1H), 7.17 (s, 1H), 2.26 (s,3H), 1.34 (s, 9H). 1,2-phenylene dibenzoate (IED1)*

δ 8.08 (dd, 4H), 7.54 (tt, 2H), 7.34-7.43 (m, 8H).3-methyl-5-tert-butyl-1,2- phenylene dibenzoate (IED2)

δ 8.08 (dd, 2H), 8.03 (dd, 2H), 7.53 (tt, 1H), 7.50 (tt, 1H), 7.38 (t,2H), 7.34 (t, 2H), 7.21 (d, 1H), 7.19 (d, 1H), 2.28 (s, 3H), 1.34 (s,9H). 3,5-diisopropyl-1,2-phenylene dibenzoate (IED3)

δ 8.08 (dd, 2H), 7.00 (dd, 2H), 7.53 (tt, 1H), 7.48 (tt, 1H), 7.39 (t,2H), 7.31 (t, 2H), 7.11 (d, 1H), 7.09 (d, 1H), 3.11 (heptat, 1H), 2.96(heptat, 1H), 1.30 (d, 6H), 1.26 (d, 6H). 3-methyl-5-tert-butyl-1,2-phenylene di(4-chlorobenzoate) (IED12)

δ 7.98 (dd, 4H), 7.36 (dd, 4H), 7.21 (s, 1H), 7.17 (s, 1H), 2.26 (s,3H), 1.34 (s, 9H). *comparative

II. Procatalyst Compositions

A procatalyst precursor is charged, according to the weight shown inTable 2, into a flask equipped with mechanical stirring and with bottomfiltration. 60 ml of a mixed solvent of TiCl₄ and chlorobenzene (1/1 byvolume) is introduced into the flask and then 2.52 mmol of internalelectron donor is added. The mixture is heated to 115° C. and remains atthe same temperature for 60 minutes with stirring at 250 rpm beforefiltering off the liquid. 60 ml of mixed solvent is added again and thereaction is allowed to continue at the same desired temperature for 60minutes with stirring followed by filtration. This process is repeatedonce. 70 ml of iso-octane is used to wash the resultant solid at ambienttemperature. After the solvent is removed by filtration, the solid isdried by N₂ flow.

TABLE 2 Procatalyst Precursor Weight MagTi-1 3.0 g SHAC ™ 310 2.0 g

MagTi-1 is a mixed Mag/Ti precursor with composition of Mg₃Ti(OEt)₈Cl₂(a MagTi precursor prepared according to example 1 in U.S. Pat. No.6,825,146) with an average particle size of 50 micron. SHAC™ 310 is abenzoate-containing catalyst (a BenMag procatalyst precursor with anaverage particle size of 27 micron) with ethyl benzoate as the internalelectron donor made according to Example 2 in U.S. Pat. No. 6,895,146,the entire content of which is incorporated herein by reference.Titanium content for each of the resultant procatalyst compositions islisted in Table 3.

Procatalyst compositions produced by way of the foregoing procedure areset forth at Table 3.

TABLE 3 Ti OEt EB Donor-1 Procatalyst # Precursor Donor-1 Donor-2 (%)(%) (%) (%) 4949-27-1 MagTi-1 DiBP 3.03 0.21 0 13.68 4949-29-2 MagTi-1DiBP 3.26 0.19 0 13.27 4949-4-2 MagTi-1 IED1 3.17 0.26 4.94 trace4949-5-2 SHAC ™ 310 IED1 3.88 0.2 1.96 trace 4949-8-2 MagTi-1 IED1 EB3.13 0.39 6.29 1.27 4949-25-1 MagT1-1 IED2 3.52 0.27 4.08 10.314949-25-2 SHAC ™ 310 IED2 3.23 0.11 2.33 10.62 4949-54-1 MagTi-1 IED34.1 0.32 5.02 8.19 4949-54-2 MagTi-1 IED3 EB 3.71 0.28 8.87 5.614949-51-3 MagTi-1 IED4 2.73 0.35 0.37 8.65 4949-51-4 MagTi-1 IED4 EB2.52 0.34 1.68 7.51 1590-29-1 MagTi-1 IED5 3.13 0.33 0.26 4.501590-29-2¹ MagTi-1 IED5 2.82 0.25 0.08 5.64 1590-29-3² MagTi-1 IED5 3.990.37 0.28 6.15 1910-27-3 MagTi-1 IED6 3.41 0.89 1.22 13.15 1910-27-4SHAC ™ 310 IED6 3.05 0.21 1.32 9.24 1590-28-1 MagTi-1 IED7 3.35 0.2 0.22NM 1590-28-3 MagTi-1 IED8 3.73 0.19 0.15 NM 1910-14-1 MagTi-1 IED9 3.190.17 0 2.56 1910-14-2 SHAC ™ 310 IED9 2.93 0.07 0.39 3.63 1910-14-3MagTi-1 IED9 MeBC 2.97 0.26 0 1.36 1910-27-1 MagTi-1 IED10 3.95 0.44 0NM 1910-16-1 MagTi-1 IED11 2.94 0.12 0 12.23 1910-16-2 SHAC ™ 310 IED113.03 0.07 0.93 7.54 1910-16-3 MagTi-1 IED12 2.76 0.16 0 12.14 1910-16-4SHAC ™ 310 IED12 1.82 0.10 0.60 8.75 ¹= IED added during a 1^(st) and a2^(nd) halogenation (TiCl₄) ²= IED added during a 1^(st), a 2^(nd), anda 3^(rd) halogenation (TiCl₄) EB = ethyl benzoate DEP = diethylphthalate DiBP = diisobutyl phthalate IED = internal electron donor(from Table 1) MeBC = p-methylbenzoyl chloride NM = not measured OEt =ethoxide % = weight percent based on total weight of the procatalystcomposition

III. Polymerization

Polymerization is performed in liquid propylene in a 1-gallon autoclaveusing separate injection. The external electron donor isn-propyltrimethoxysilane (NPTMS) or dicyclopentyldimethoxysilane(DCPDMS). After conditioning, the reactor is charged with 1375 g ofpropylene and a desired amount of hydrogen and brought to 62° C.External electron donor, a solution of 0.27-M triethylaluminum iniso-octane, and a suitable amount of 5.0-wt % catalyst slurry in mineraloil (as indicated in data tables below) are premixed in the same vialfor 20 minutes at room temperature and then charged into the reactorfollowed by isooctane flushing using a high pressure catalyst injectionpump to initiate the polymerization. After the exotherm, the temperatureis controlled to 67° C. Run time is 1 hour.

Reference catalyst performance and resultant polymer properties areprovided in Table 4.

TABLE 4 Procat- Activity Bulk Melt Donor- Donor- alyst TEAl Al/ H₂ (kg/Density Flow XS T_(M(F)) Procatalyst # Precursor 1 2 EED (mg) (mmol) EED(scc) g-h) (g/cc) (g/10 min) (%) PDI (° C.) 4949-27-1 MagTi-1 DiBP NPTMS11.6 2 8  800 15.9 0.32  3.1 2.4 3.81 170.17 DCPDMS 11.6 2 8  1250 25.50.38  2.4 3.5 4.54 172.15 4949-29-2 MagTi-1 DiBP DCPDMS 16.7 2 8  150032.9 0.37  1.8 3.9 4.68 171.92 DCPDMS  8.4 2 8  1500 30.1 0.37  2.3 3.84.67 172.27 DCPDMS  8.4 2 8 10000 21.3 0.33 26.8 2.3 5.29 171.24 DCPDMS 8.4 2 8 15000 16.8 0.31 43.2 1.8 5.41 171.19 DCPDMS  8.4 2 8 20000 22.90.33 74.2 1.8 5.26 170.81 NPTMS 16.7 2 8  1000 26.5 0.35  3.1 2.8 3.89170.25 NPTMS  8.4 2 8  1000 12.4 0.33  3.7 2.4 4.14 170.4  NPTMS  8.4 28  7000 14.3 0.32 43.4 2.3 4.63 169.76 NPTMS  8.4 2 8 12000 12.1 0.3089.4 2.4 4.57 169.41 4949-4-2 MagTi-1 IED1 EB DCPCMS 17.4 2 4  1500 20.90.40  3.1 7.2 6.24 NPTMS 17.4 2 4  1000 10.7 0.42  3.5 6.5 5.09 4949-5-2SHAC ™ IED1 DCPDMS 17.4 2 4  1500 15.6 0.39  4.3 8.1 5.64 310 NPTMS 17.42 4  1000  9.1 0.36  3.6 8.1 4949-8-2 MagTi-1 IED1 EB DCPDMS 17.4 2 4 1500 17.4 0.39  5.2 7.8 5.90 170.16 NPTMS 17.4 2 4  1000  9.1 0.38  5.26.8 4.71 169.35 DCPDMS = dicyclopentyldimethoxysilane DiBP -diisobutylphthalate EB = ethyl benzoate EED = external electron donorIED = internal electron donor (Table 1) NPTMS = n-propyltrimethoxysilane

Catalyst performance and resultant polymer properties for catalystscontaining phenylene dibenzoate substituted at the 3,5-positions areprovided in Table 5.

TABLE 5 Melt Bulk Flow Donor- Donor- Procatalyst TEAl Al/ H₂ ActivityDensity (g/10 XS T_(M(F)) Procatalyst # Precursor 1 2 EED (mg) (mmol)EED (scc) (kg/g-h) (g/cc) min) (%) PDI (° C.) 4949-25-1 MagTi-1 IED2DCPDMS 8.4 2 8  2500 51.2 0.25 1.2 2.2 5.56 172.19 DCPDMS 8.4 2 8  500059.4 0.27 3.3 2.4 5.62 171.95 DCPDMS 8.4 2 8 10000 39.6 0.28 14.4 1.85.43 171.39 DCPDMS 8.4 2 8 15000 42.6 0.29 34.9 1.5 5.26 171.02 DCPDMS8.4 2 8 20000 53.2 0.31 112.6 1.1 5.36 170.09 4949-25-2 SHAC ™ IED2DCPDMS 11.6 2 8  1250 25.3 0.39 1.1 4.5 6.31 171.86 310 NPTMS 11.6 2 8 800 22.3 0.40 0.7 2.5 NPTMS 11.96 2 8  8000 20.3 0.40 77.2 3.1 4.79170.17 4949-54-1 MagTi-1 IED3 DCPDMS 4.8 2 8  1500 49.9 0.25 0.8 2.9DCPDMS 8.4 2 8  2500 45.2 0.25 1.9 3.2 6.04 171.00 DCPDMS 8.4 2 8  500053.3 0.25 4.4 3.4 5.98 171.23 DCPDMS 8.4 2 8 10000 34.0 0.26 18.8 2.15.85 170.74 DCPDMS 8.4 2 8 15000 56.2 0.30 50.9 1.9 5.47 170.69 DCPDMS5.9 2 8 20000 44.7 0.28 111.6 1.7 4.37 170.15 4949-54-1 MagTi-1 IED3 EBDCPDMS 4.8 2 8  1500 45.1 0.27 0.8 3.4 DCPDMS 8.4 2 8  2500 48.2 0.291.7 2.1 6.27 171.42 DCPDMS 5.9 2 8  5000 54.0 0.27 5.6 1.9 6.14 171.31DCPDMS 5.9 2 8 10000 48.7 0.25 23.4 2.0 5.84 170.87 DCPDMS 5.9 2 8 1500040.7 0.28 75.7 2.5 5.39 170.24 DCPDMS 5.9 2 8 20000 27.5 0.28 97.8 1.24.48 170.25 DCPDMS = dicyclopentyldimethoxysilane EB = ethyl benzoateEED = external electron donor IED = internal electron donor (Table 1)NPTMS = n-propyltrimethoxysilane

Catalyst performance and resultant polymer properties for catalystscontaining phenylene dibenzoate substituted at the 3,6-positions areprovided in Table 6.

TABLE 6 Bulk Melt Donor- Donor- Procatalyst TEAl Al/ H₂ Activity DensityFlow XS T_(M(F)) Procatalyst # Precursor 1 2 EED (mg) (mmol) EED (scc)(kg/g-h) (g/cc) (g/10 min) (%) PDI (° C.) 4949-51-3 MagTi-1 IED4 NPTMS16.7 2 8 1000 17.1 0.35 1.6 1.6 4.42 171.78 DCPDMS 16.7 2 8 1500 19.30.35 1.8 3.0 5.07 171.99 4949-51-4 MagTi-1 IED4 EB NPTMS 16.7 2 8 100012.8 0.34 1.7 1.8 4.61 171.38 DCPDMS 16.7 2 8 1500 16.7 0.32 2.5 3.45.21 171.83 DCPDMS = dicyclopentyldimethoxysilane EB = ethyl benzoateEED = external electron donor IED = internal electron donor (Table 1)NPTMS = n-propyltrimethoxysilane

Catalyst performance and resultant polymer properties for catalystscontaining phenylene dibenzoate substituted at the 4-position areprovided in Table 7.

TABLE 7 Bulk Melt Donor- Donor- Procatalyst TEAl Al/ H₂ Activity DensityFlow XS Tm(f) Procatalyst # Precursor 1 2 EED (mg) (mmol) EED (scc)(kg/g-h) (g/cc) (g/10 min) (%) PDI (° C.) 1590-29-1 MagTi-1 IED5 NPTMS16.7 2 8 3000 25.0 0.38  6.7 4.96 5.22 169.62 DCPDMS 16.7 2 8 4500 33.20.37 11.4 5.48 6.37 170.43 1590-29-2 MagTi-1 IED5 NPTMS 16.7 2 8 300018.6 0.33  2.6 3.27 7.05 169.87 DCPDMS 16.7 2 8 4500 26.7 0.35  3.5 4.437.80 170.91 1590-29-3 MagTi-1 IED5 NPTMS 16.7 2 8 3000 10.4 0.30  2.72.98 7.26 171.34 DCPDMS 16.7 2 8 4500 13.7 0.31  4.1 3.56 7.55 171.401590-29-4 SHAC ™ IED5 NPTMS 16.7 2 8 3000 18.5 0.37  7.2 5.96 6.40169.63 310 DCPDMS 16.7 2 8 4500 28.1 0.37  9.1 7.60 7.23 170.351910-27-3 MagTi-1 IED6 NPTMS  8.4 2 8 3000 40.0 0.26  2.1 1.63 5.36170.85 DCPDMS  8.4 2 8 4500 43.3 0.28  1.3 2.37 5.95 172.11 1910-27-4SHAC ™ IED6 NPTMS 16.7 2 8 3000 27.8 0.39  1.7 3.22 6.09 171.20 310DCPDMS 16.7 2 8 4500 28.9 0.40  3.8 5.21 7.17 171.26 DCPDMS =dicyclopentyldimethoxysilane EED = external electron donor IED =internal electron donor (Table 1) NPTMS = n-propyltrimethoxysilane

Catalyst performance and resultant polymer properties for catalystscontaining fused aromatic phenylene dibenzoate are provided in Table 8.

TABLE 8 Bulk Melt Donor- Donor- Procatalyst TEAl Al/ H₂ Activity DensityFlow XS Tm(f) Procatalyst # Precursor 1 2 EED (mg) (mmol) EED (scc)(kg/g-h) (g/cc) (g/10 min) (%) PDI (° C.) 1590-28-1 MagTi-1 IED7 NPTMS16.7 2 8 3000 24.0 0.30 15.1 5.69 4.51 168.76 DCPDMS 16.7 2 8 4500 34.30.32  9.6 7.16 5.72 170.14 1590-28-2 SHAC ™ IED7 NPTMS 16.7 2 8 300020.7 0.34 19.0 8.45 4.97 168.93 310 DCPDMS 16.7 2 8 4500 26.0 0.34 19.58.63 6.13 169.88 1590-28-3 MagTi-1 IED8 NPTMS 16.7 2 8 3000 25.5 0.32 6.8 4.06 4.98 169.65 DCPDMS 16.7 2 8 4500 20.3 0.30  3.9 3.97 6.01171.26 1590-28-4 SHAC ™ IED8 NPTMS 16.7 2 8 3000 16.3 0.34  6.1 5.236.26 169.96 310 DCPDMS 16.7 2 8 4500 32.0 0.36  6.1 7.61 7.45 170.47DCPDMS = dicyclopentyldimethoxysilane EED = external electron donor IED= internal electron donor (Table 1) NPTMS = n-propyltrimethoxysilane

Catalyst performance and resultant polymer properties for catalystscontaining substituted phenylene diesters of substituted benzoic acidsare provided in Table 9.

TABLE 9 Bulk Donor Donor Procatalyst TEAl Al/ H₂ Activity Density MeltFlow XS Tm(f) Procatalyst # Precursor -1 -2 EED (mg) (mmol) EED (scc)(kg/g-h) (g/cc) (g/10 min) (%) PDI (° C.) 1910-14-1 MagTi-1 IED9 NPTMS16.7 2 8 3000 23.9 0.31  3.7 2.96 5.15 170.20 DCPDMS 16.7 2 8 4500 30.40.32  4.0 3.71 5.96 170.61 1910-14-2 SHAC ™ IED9 NPTMS 16.7 2 8 300030.2 0.39  2.1 3.11 6.14 172.48 310 DCPDMS 16.7 2 8 4500 32.2 0.39  2.74.18 6.33 171.65 1910-14-3 MagTi-1 IED9 MeBC NPTMS 16.7 2 8 3000 20.30.29  9.5 4.58 4.84 169.45 DCPDMS 16.7 2 8 4500 24.7 0.29  5.7 4.93 6.141910-27-1 MagTi-1 IED10 NPTMS 16.7 2 8 3000 27.1 0.27 19.1 3.60 5.22170.01 DCPDMS 16.7 2 8 4500 32.4 0.33 18.7 4.42 4.99 170.20 1910-27-2SHAC ™ IED10 NPTMS 16.7 2 8 3000 27.6 0.35 23.8 6.12 4.97 169.55 310DCPDMS 16.7 2 8 4500 34.3 0.36 20.1 6.87 5.52 170.23 1910-16-1 MagTi-1IED11 DCPDMS 16.7 2 8 4500 31.44 0.24  2.0 2.05 5.19 171.97 NPTMS  8.1 28 3000 34.3 0.33  1.6 0.86 5.11 171.71 1910-16-1 SHAC ™ IED11 DCPDMS16.7 2 8 4500 31.4 0.24  2.0 2.05 5.19 171.97 310 NPTMS 16.7 2 8 300029.2 0.41  1.9 1.55 6.07 171.95 1910-16-3 MagTi-1 IED12 NPTMS 16.7 2 83000 26.9 0.31  0.7 0.71 5.41 171.22 DCPDMS 16.7 2 8 4500 34.2 0.32  1.01.73 5.64 171.03 1910-16-4 SHAC ™ IED12 NPTMS 16.7 2 8 3000 30.8 0.40 1.0 1.39 5.83 170.89 310 DCPDMS 16.7 2 8 4500 31.2 0.40  1.8 2.47 5.70171.29 DCPDMS = dicyclopentyldimethoxysilane EED = external electrondonor IED = internal electron donor (Table I) MeBC = p-methylbenzoylchloride NPTMS = n-propyltrimethoxysilane

The results show that catalyst compositions with substituted phenylenearomatic diester with different structural variety significantly improvecatalyst activity, stereoselectivity (XS), molecular weight distribution(PDI), and/or polymer crystallinity (Tm(f)), compared to catalystscompositions containing (i) unsubstituted 1,2-phenylene dibenzoateand/or (ii) phthalate (Table 4). Internal electron donors containingsubstituted phenylene aromatic dibenzoate can be used with differenttypes of precursors (such as MagTi and BenMag, in particular) toadvantageously provide improved catalyst performance and polymers withimproved properties. The inclusion of a second internal electron donor,such as ethyl benzoate (EB) or p-methylbenzoyl chloride (MeBC), eitherfrom direct addition during catalyst preparation or from the procatalystprecursor, broadens molecular weight distribution. In addition, multipleadditions of the internal electron donor, as demonstrated by IED5,improve catalyst stereoselectivity.

It is specifically intended that the present disclosure not be limitedto the embodiments and illustrations contained herein, but includemodified forms of those embodiments including portions of theembodiments and combinations of elements of different embodiments ascome within the scope of the following claims.

1. A procatalyst composition comprising: a combination of a magnesiummoiety, a titanium moiety and an internal electron donor comprising asubstituted phenylene aromatic diester having the structure (I)

wherein R₁-R₁₄ are the same or different, and at least one of R₁-R₄ isselected from the group consisting of a substituted hydrocarbyl grouphaving 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group having 1to 20 carbon atoms, a halogen, and combinations thereof.